Method for the production of barium chlorid



1. H. MACMAHON. METHOD FOR THE PRODUCTION 0F BARIUM GHLORID.

. v APPLICATION FILED IAN-20| 1920. "1' ,$78,594.

APmnwd my 17,1921.

#Sioux I N VEN TOR.

WITNESS:

ATTORNEYS.

`tion takes place,

waste in the form of calcium chlorid.. My invention therefore has anespecial utility in barytes or barium inexpensively solution a chemicalnnss n. mounnoir,

i immrwonxs,

or snrmrnvmemu, nssicnon 'ro m na'rnmsou INC., ii coaronn'rion or minionron 'ran rnonuc'rioiv or snaren ennemi).

To all whomt may concem:

Be it known that I, JAMES I-I. MAoMAHoN,

a citizen of the United States, residin at Saltville, in the county ofSmyth and tate of Virginia, have invented certain new and usefulImprovements in Methods for the Production of Barium Chlorid, of whichthe following is a full, clear, and exact description.- l i i Inaccordance with this invention barium chlorid, which is' so largely usedin the production of other barium salts, may be abundantly produced atrelatively small cost.. I-Ieretofore a 'common' method of preparingbarium chlorid has been to dissolve barium carbonate in hydrochloricacid. lI have discovered a method of producing it `froin the black ashobtained by reducing the mineral sulfate with coal dust, as b calciningin al black ash which contains from sixty to seventy-five percentofbarium sulid may be obtained in large quantities and-it is therefore anabundant and cheap source 'of barium suld which is obtained from theblack ash by lixiviation. By my method I convert this chea pound atcomparatively litt e vcost into the valuable product,barium chlorid,

I have discovered that when barium sulid and ammonium chlorid are mixedtogether reaction takes lace, barium chlorid and ammonium sulfid eingformed in) accordance with the following reaction:

If the temperature of the solution be sufficiently hot (80 or 90 C.)when the reacthe ammonium sulfidas a'gas,`and the barium formed passesoif of the blow-of chlorid may be slparated out li uor by crystaization. f

he commercial value of this discovery is considerably enhanced by reasonof the fact uantities of ammonium chlorid are avai ab e in from theammonia soda process, the chlorin content4 of which has heretofore goneto the treatment ofthis particular liquor, and

will be explained by way of, illustration Speccation of LettersIlatent.`

suitable furnace. This barium com-- 'weak liquor in ta finto a strong vbarium the feeder liquor resulting Patented May i7, 1921.

Application nled January 20,1920. 'Serial No. 352,860.

when` so employed, but it understood that my'invention is broadlyapplicable to the treatment of any ammonium chlorid solution to utilizethe chlorin therein to form barium chlorid.

In the accompanying drawing, I have shown a diagram of an a paratusincluding receptacles and connections, suitable for carrying out myinvention in connection with the feederliquorfrom the ammonia i sodaprocess. Y The feeder liquor from the sodium bicarbonate iilters whichconsists principally of ammonium chlorid together with some ammoniumbicarbonate, enters the top section ofthe ammonium chlorid still A. Inthe passage of the liquor down the still the volatile ammoniumbicarbonate is driven off by the exhaust steam which enters the bottomsection of the still and isreturned to the ammonia 'soda process. Theliquor which now contains vammonium chlorid and sodium chlorid leavesthe bottom of the still and is conducted into the tank A1 from which itis pumped intov the ammonium chlorid evaporator A2. In this vessel theliquor is concentrated' until substantially all of the sodium chlorid isthrown out of solution. The sodium chlorid is drawn from vthe vbottom ofthe evaporator to the centrifugal machine M where it is washed anddried, the from this machine going back 'to the ammonium chloridV evaorator A2. The strong'ammonium chlorid iquor overiows into the ammoniumchlorid crystalliz- 'pan A3. The ammonium chlorid cryss are then takenfrom this pan and made solution in the vessel A4,

The .black ash or crude barium sulfid is leachedin the black ashlixiviators B1, the clear concentrated solution bein stored `in thestock'tankBT The reaction etween the sulfid and ammonium chlorid bywhich barium chlorid and ammonium suld chlorid still The barium sulidand ammonium chlorid solutions are pumped from their respectivel tanks,B2 and A4, into the top section of the still.` Exhaust steam enters theliquori passing monium sulid as a gas from the liquor, and may betreated to recover the free ammonia therefrom.

down the still. The amis thereby caused to pass oif f y liquordischarging from the bottom of the stlll into caustic pots where it willbe evaporated until it containsr about 60% of sodium suliid.

The barium chloridsolution with a small quantity of ammoniumchloridinexcess, to insure the complete decomposltlon of the barium sulfid is runfrom the bottom section of still to the barium chlorid tank B3.Fromvthis tank it is Eumped to the barium chlorid evaporator 4, where itis concentrated by steam, the strong llquor overflowing to thecrystallizing pan B5. The mother liquor from this pan is returned againto the process, the barium chlorid` crystals being washed and dried.

In some cases it may be preferable to treat the feeder liquor directfrom the sodium bicarbonate filters without first separating the sodiumchlorid, and separate the barium chlorid from the sodium chlorid, by cstallization, although generally the diiicllilt of separating the bariumchlorld and so iumchlorid makes it preferable to rst separate the sodiumchlorid from the ammonlum chlorid liquor before reactlon Vwith thebarium sulf The reaction between the barium sulid and the ammoniumchlorid is quantitative.

Owing tothe practical diiiiculty of exactly balancing the reagents, oneor the other of the reacting substances will nearly always be in excess,and iti-is usually preferable that the ammonium-.chlorid should be inexcess, as above mentioned. However, it will be understood that thebarium suliid may be used in excess, in which case the blow-off liquormay be treated with hydrochlorid acid to complete the decompositionofthe barium ld. i

I claim:

1'. The method p chlorid consisting in separating the ammonium chloridfrom the feeder liquor of the ammonia soda process, dissolving .theammonium chlorid crystals so obtained, mixing a solution of barium -suldwith the ammonium chlorid solution, forming barium chlorid Aand.ammonium suld, and then se arating the barium chlorid from the liquor ycrystallization. 4

2.7The method of producing barium chlorid 'consistin in concentratingthe feeder liquor'of the ammonia soda process substantially all the ofproducing barium y evaporation until sodium chlorid is thrown out ofsolution, drawing off the sodium chlorid, separating the ammoniumchlorid from the strong ammonium chlorid liquor by crystallization,dissolving the ammonium chlorid crystals so obtained, mixing a solutionof barium chlorid with the ammonium chlorid solution,

forming barium chlorid and ammonium sulmixing the .solution of bariumsulfid with the ammonlum chlorid solution, formin barium chloridandammonium suld, and then separating the barium chlorid liquor byIcrystallization.

he method of producing barium chlorid consisting in lixivating the blackash of barytes to form a concentrated solution of barium sulfid,lconcentrating the from the feeder liquor of the ammonla soda process byevaporation until 'substantially all the sodium chlorid is thrown out ofsolution, drawing off the sodium chlorid, separating the ammoniumchlorid from Vthestrong ammonium chlorid liquor by crystallization,dissolving the ammonium chlorld crystals so obtained, mixing. thesolution of barium sulfid with the ammonium chlorid' solution, formingbarium chlorid and ammonium sulfid, heatingsuiiciently to drive off theammonium sulfid, and then vseparating the barium chlorid from the liquorby crystallization. l

5. The method of making barium chlorid consisting in concentrating thefeeder liquor of the ammonia soda process until the major portion of thecontained sodium chlorid is thrown out of solution, removing the sodiumchlorid thus thrown out, then reacting upon the feeder. liquor withbarium suld to produce barium chlorid and ammonium-sulfid, andseparating the barium chlorid and. ammonium sulfid.

6. The method of makinabarium chlorid consisting in treating the feederliquor of the ammonia soda process to remove the maJor portion f\ of thecontained sodium chlorid, then reacting upon the feeder liquor withbarium sulfid 1n the presence of sufficient heat to produce bariumchlorid in sqllution and ammonium sulfid in the vapor p ase.

7. The method of making barium chlorid consisting in concentrating thefeeder liquor of the ammonia soda process to throw out of solution themajor portion of the sodium chlorid content, l.removing the sodiumchlorid from the feeder liquor, then react- InV ing upon the li uor withbarium suld with the feeder liquor sufficiently in excess to insure thecomplete decomposition of the barium sulfid and producing barium chloridand ammonium sulfid, and then isolating the barium chlorid.

8. The method of making barium chlorid consisting in treating theammonium soda rocess to remove the major portion of t e contained sodiumchlorid, then reacting upon the feeder liquor the feeder liquor of withbarium suld to produce barium chlorid and ammonium sulfid, the feederliquor in the last vreaction being slightly in excess of the amountnecessary to combine With the barium suld in order to insure thecomplete decomposition of the barium sulid and then separating thebarium chlorid from the resultant liquor.

.In witness whereof 1 hereunto subscribe my signature.

- JAMES H. MACMAHON.

